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A simple method for production of pure silica from rice hull ash
U. Kalapathy a,*, A. Proctor a, J. Shultz b
b
a
Department of Food Science, University of Arkansas, 272 Young Ave, Fayetteville, AR 72704 ,USA
Arkansas Analytical Laboratory, High Density Electronics Center, University of Arkansas, Fayetteville, AR 72701, USA
Received 8 October 1998; received in revised form 2 September 1999; accepted 2 September 1999
Abstract
Rice hull ash (RHA), a waste product of the rice industry is rich in silica. A simple method based on alkaline extraction followed
by acid precipitation was developed to produce pure silica xerogels from RHA, with minimal mineral contaminants. The silica gels
produced were heated to 80o C for 12 h to obtain xerogels. Silica and mineral contents of xerogels were determined by energy
dispersive X-ray (EDX) and inductively-coupled plasma (ICP) emission spectrometers, respectively. Xerogels produced from RHA
had 93% silica and 2.6% moisture. The major impurities of silica produced from RHA at an extraction yield of 91% were Na, K, and
Ca. Acid washing prior to extraction resulted in silica with a lower concentration of Ca (<200 ppm). However, nal water washing
of the xerogel was more eective in producing silica with lower overall mineral content (Na < 200 ppm and K < 400 ppm). X-ray
diraction patterns revealed the amorphous nature of silica xerogel. Fourier transform infrared (FTIR) data indicated the presence
of siloxane and silanol groups. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Rice hull ash; Silica xerogels; Minerals
1. Introduction
Burning rice hull as fuel to generate energy results in
the waste product, rice hull ash (RHA). RHA is rich in
silica (about 60%) and can be an economically viable
raw material for production of silica gels and powders
(Kamath and Proctor, 1998; Chakraverty and Kaleemullah, 1991). RHA has been evaluated as an adsorbent of minor vegetable oil components (Proctor et al.,
1995; Proctor and Palaniappan, 1990). Although various uses for rice hull and RHA have been suggested in
the literature, their disposal or utilization remains a
major concern.
Soluble silicates produced from silica are widely used
in the glass, ceramics, and cement as a major component
and in pharmaceuticals, cosmetics, and detergents industries as a bonding and adhesive agents (Anon., 1997;
Laxamana, 1982). Silica also has been used as a major
precursor for a variety of inorganic and organometallic
materials which have applications in synthetic chemistry
as catalysts, and in thin lms or coatings for electronic
and optical materials (Lender and Ruiter, 1990; Brinker
*
Corresponding author. Tel.: +1-501-575-4605; fax: +1-501-5756936.
0960-8524/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 9 9 ) 0 0 1 2 7 - 3
258
2. Methods
The silicon content of the samples was estimated using energy dispersive X-ray (EDX) spectroscopy (Kevex
Instruments, Valencia, CA). Mineral content of the xerogels was determined by nitric acid digestion followed
by atomic emission measurements using ICP emission
spectroscopy (Spectro Analytical Instruments, Fitsburg,
MA).
X-ray diraction patterns were obtained by a dual
goniometer Xpert XRD system (Philips Electronic Instruments, The Netherlands) using an acceleration
voltage of 40 kV and current of 45 mA. The diraction
angle was scanned from 10o to 90o 2h, at a rate of 5o /
min. Fourier transform infrared (FTIR) data were obtained by adding 100 interferograms using a Impact 410
Nicolet instrument (Analytical Instruments, Madison,
WI).
259
was estimated from the EDX data based on the assumption that all of the silicon was in the form of silica.
The silica and moisture contents of xerogels produced
from unwashed RHA were 93% and 2.7%, respectively.
Compositions of minerals leached from RHA by acid
washing at pH 1, 3, 5, and 7 are shown in Table 1. Since
acid leaching at a pH of 1 was found to be more eective
in removing Ca, Fe, and Mn from RHA, a washing step
at pH 1 was used in all subsequent acid leaching treatments. Unwashed RHA, and RHA washed at pH 7 were
used as controls to evaluate the eectiveness of acid
washing on the purity of the xerogel. The eect of acid
leaching and nal washing of xerogel on the mineral
content of RHA silica is shown in Table 2. Trace metal
ions such as polyvalent iron and manganese with 3+,
and 4+ charges, respectively, might have been strongly
adsorbed onto silica surface and subsequently trapped
inside the silica network during gel formation from silicate solution (Iler, 1979). As a result of this, Fe and Mn
might not be completely solubilized during the nitric
acid digestion for ICP measurements. The Fe and Mn
concentrations in the silica would be aected by the
factors such as surface area, porosity, and particle size
Table 1
Mineral content of acid solubles from RHA
Minerals
pH 3
pH 5
pH 7
Sodium (%)
Potassium (%)
Calcium (%)
Magnesium (%)
Iron (ppm)
Manganese (ppm)
2.42a
29.5a
8.14a
2.57a
3204a
19745a
1.97a
31.7a
7.03a
2.85a
539b
1557c
1.81a
39.4a
2.77b
2.05a
20c
2228c
1.90a
37.5a
3.93b
2.41a
17c
5823b
260
Table 2
Mineral content of silica prepared from rice hull ash using various treatments
Minerals
Sodium (%)
Potassium (%)
Calcium (%)
Magnesium (%)
Iron (ppm)
Manganese (ppm)
Treatments
1
4.486b
0.266a
0.047a
0.008a
19.8
<1
7.120a
0.133b
0.037a
0.007a
33.7
<1
6.577a
0.164b
0.018b
0.002a
14.3
<1
0.019c
0.036c
0.047a
0.007a
34.6
<1
0.021c
0.039c
0.019b
0.006a
32.2
<1
Treatment 1 Silica was prepared from unwashed RHA. Treatment 2 Silica was prepared from RHA washed at pH 7. Treatment 3 Silica
was prepared from acid washed RHA. Treatment 4 Silica was prepared from unwashed RHA and washed after silica was dried. Treatment 5
Silica was prepared from acid washed RHA and washed after silica was dried.
*
Values are means of triplicate analyses. In each row, values with dierent superscripts are signicantly (P < 0.05) dierent from each other. Average
standard deviations of Na, K, Ca, and Mg, measurements were 0.5%, 0.1%, 0.01%, and 0.001%, respectively.
**
See the note in Section 3 regarding Fe and Mn measurements.
As shown in Fig. 4, the broad X-ray diraction pattern of RHA silica, which is typical for amorphous
solids (Kamath and Proctor, 1998), conrmed the ab-
261
Table 3
Eect of concentration of sodium hydroxide used for silica extraction
on the yield of silica
Extraction
0.1 NaOH
0.25 N NaOH
0.5 N NaOH
1.0 N NaOH
Not extracted
17c
35b
91a
*
Values are means of triplicate measurements. Values with dierent
superscripts are signicantly (P < 0.05) dierent from each other.
Average standard deviation of silica yield was 2.3%.
Table 4
Yield and moisture content of silica from washed and unwashed rice
hull ash (RHA)
RHA
Yield of silica
(%)
Moisture content
(%)
Acid washed
Washed at pH 7
Unwashed
91a
91a
89a
2.6a
2.4a
2.7a
*
Values are means of triplicate measurements. In each column, values
with similar superscripts are not signicantly (P < 0.05) dierent from
each other. Average standard deviations of silica yield (%) and moisture contents (%) were 4 and 0.5, respectively.
4. Conclusions
This study revealed that silica xerogels with 93% silica
content and minimal mineral contaminants can be
produced from RHA using a simple low energy chemical
method. The silica extraction yield from RHA was 91%.
The initial acid washing of RHA resulted in a lower Ca
content in the silica xerogel. The nal washing of the
xerogel led to a silica product with lower Na, and K
contents. Incorporation of initial acid washing of RHA
and nal washing of the xerogel resulted in a pure silica
with total Na, K, and Ca contents of <0.1%.
Acknowledgements
We wish to thank Producers Rice Mill (Stuttgart,
AR) for providing RHA; and Bruce Cottingham,
(Tyson Foods, Springdale, AR) for his assistance during
this study.
References
262
Mizuki, E., Okumura, S., Saito, H., Muro, S., 1993. Formation of
silicon carbide from rice husks using enzymatic methods for carbon
control. Biores. Technol. 44, 4751.
Proctor, A., 1990. X-ray diraction and scanning electron microscope
studies of processed rice hull silica. J. Am. Oil Chem. Soc. 67,
576584.
Proctor, A., Clark, P.K., Parker, C.A., 1995. Rice hull ash adsorbent
performance under commercial soy oil bleaching conditions.
J. Am. Oil Chem. Soc. 72, 459462.
Proctor, A., Palaniappan, S., 1990. Adsorption of soy oil free fatty
acids by rice hull ash. J. Am. Oil Chem. Soc. 67, 1517.